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US20080183000A1 - Glycerol ester-free functionalized vegetable oil derivatives and their latex compositions - Google Patents

Glycerol ester-free functionalized vegetable oil derivatives and their latex compositions Download PDF

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Publication number
US20080183000A1
US20080183000A1 US11/699,693 US69969307A US2008183000A1 US 20080183000 A1 US20080183000 A1 US 20080183000A1 US 69969307 A US69969307 A US 69969307A US 2008183000 A1 US2008183000 A1 US 2008183000A1
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Prior art keywords
meth
acrylate
oil
acrylate monomer
fatty amide
Prior art date
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Abandoned
Application number
US11/699,693
Inventor
Shelby F. Thames
James W. Rawlins
Sharathkumar K. Mendon
David Delatte
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University of Southern Mississippi
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Individual
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Filing date
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Priority to US11/699,693 priority Critical patent/US20080183000A1/en
Assigned to UNIVERSITY OF SOUTHERN MISSISSIPPI, THE reassignment UNIVERSITY OF SOUTHERN MISSISSIPPI, THE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: THAMES, SHELBY F., RAWLINS, JAMES W., DELATTE, DAVID, MENDON, SHARATHKUMAR K.
Priority to EP08724868A priority patent/EP2114866A2/en
Priority to PCT/US2008/001088 priority patent/WO2008094503A2/en
Publication of US20080183000A1 publication Critical patent/US20080183000A1/en
Priority to US12/331,115 priority patent/US8450414B2/en
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/24—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
    • C09D177/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C08L77/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids

Definitions

  • the present invention is directed to vegetable oil derivatives. More particularly, the present invention is directed to functionalized vegetable oil derivative macromonomers that can be used in latexes and coatings.
  • a key problem encountered by coatings manufacturers is the development of coating formulations with low volatile organic compound (VOC) content.
  • emulsion polymers are currently formulated with coalescing aids or plasticizers in order to form films at and below ambient conditions yet dry to films of sufficient glass transition temperature (T g ) to perform adequately at and above room temperature.
  • T g glass transition temperature
  • the coalescing aids evaporate upon application and constitute VOCs.
  • MFT minimum film temperature
  • Low MFT polymers are required in order to exhibit coalescence, flow, and surface wetting properties.
  • the coatings are not usable. Therefore, it is necessary to develop a technology in which coating formulations contain suitable ingredients to provide an initial low MFT, which, upon application, form non-tacky, durable, hard, and water resistant surfaces having a T g significantly above their MFT.
  • compositions which cure under ambient conditions are known in the prior art.
  • a few such examples involve curing by a chemical reaction such as epoxide-carboxylic acid reaction, isocyanate-moisture reaction, polyaziridine-carboxylic acid reaction, and activated methylene-unsaturated acrylic reaction.
  • VOMMs with more hydrophilicity to facilitate/promote VOMM diffusion through the aqueous phase.
  • long-term storage stability of monomers and polymers is decreased when monomers are synthesized with glycerol esters as esters are susceptible to hydrolysis. It would thus be an additional benefit to synthesize the monomers in the absence of glycerol ester groups to increase long term stability for monomers and polymers.
  • the present invention is directed to functionalized vegetable oil derivatives which are useful in latexes and coatings.
  • an ethylenically unsaturated vegetable oil is reacted with ethanolamine or substituted ethanolamines to form the hydroxy functional fatty amide.
  • the modified vegetable oil is then reacted with (meth)acryloyl chloride, or the corresponding (meth)acrylic acid to form a fatty amide(meth)acrylate monomer.
  • the modified vegetable oil can be reacted with the product of the reaction of hydroxyethyl(meth)acrylate reacted with isophorone diisocyanate to form a urethane fatty amide(meth)acrylate monomer.
  • the functionalized vegetable oil derivatives can be formulated into latexes and other coating compositions.
  • the present invention provides vegetable oil derivatives that are more hydrophilic than vegetable oils and are designed specifically for efficient random emulsion copolymerization. Specifically, the present invention provides glycerol ester-free fatty amide(meth)acrylate monomers.
  • the present invention is directed to a fatty amide(meth)acrylate monomer of the formula:
  • the present invention is also directed to a latex polymer comprising the polymerization product of an ethylenically unsaturated monomer suitable for forming a latex composition and the modified fatty amide monomer.
  • the present invention also provides a method of making a modified fatty amide monomer comprising the reaction product of a vegetable oil and ethanolamine or substituted ethanolamine; and a (meth)acrylate selected from the group comprising: (meth)acryloyl chloride, (meth)acrylic acid, and the product of hydroxyethyl(meth)acrylate reacted in equimolar proportion with isophorone diisocyanate.
  • the present invention is directed to a series of vegetable oil macromonomers and their use in latexes and coatings.
  • the invention is also directed to the method of producing these macromonomers.
  • the monomers are derived by reacting unsaturated vegetable oils with ethanolamine or substituted ethanolamine.
  • the vegetable oil derivative is then reacted with either (meth)acryloyl chloride or (meth)acrylic acid to form a fatty amide(meth)acrylate monomer or the product of the reaction of hydroxyethyl(meth)acrylate reacted with isophorone diisocyanate to form a urethane fatty amide(meth)acrylate monomer.
  • a vegetable oil such as soybean oil, coconut oil, or linseed oil is reacted with ethanolamine (or substituted ethanolamine) followed by reaction with (meth)acryloyl chloride or (meth)acrylic acid to form the fatty amide(meth)acrylate monomer.
  • substituted ethanolamines include N-methyl ethanolamine, N-oleoylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-tert-butylethanolamine, N-(tert-butoxycarbonyl)ethanolamine, N-(allyloxycarbonyl) ethanolamine, benzyl N-(2-hydroxyethyl)carbamate, ethyl-N-(2-hydroxyethyl)-carbamate, and diethanolamine.
  • the reaction mechanism is schematically shown in Reaction 1.
  • Any vegetable oil can be used in the present invention.
  • linseed oil, soybean oil and coconut oil are preferred.
  • Various compounds can be used to modify the fatty amide. Examples include but are not limited to (meth)acryloyl chloride and (meth)acrylic acid.
  • urethane fatty amide monomers are synthesized.
  • hydroxyethyl(meth)acrylate is reacted with isophorone diisocyanate.
  • the hydroxyl(meth)acrylate is reacted in equimolar proportion with isophorone diisocyanate.
  • a vegetable oil for example, soybean oil, coconut oil, or linseed oil is reacted with ethanolamine (or substituted ethanolamine) to form the hydroxyl functional fatty amide.
  • the products of the two reactions were reacted to form the urethane fatty amide(meth)acrylate monomer schematically shown in Reaction 2.
  • the macromonomers of the present invention can be used to make latexes and coatings compositions.
  • the monomers described in this patent application can be polymerized in a single or multi- stage emulsion polymerization process to include macroemulsion, miniemulsion, microemulsion and processing can be batch, semi-batch or continuous. Although it is possible to use this monomer in a staged emulsion polymerization, as disclosed in published U.S. Application 2003/0045609, the teachings of which are hereby incorporated by reference, it is not a requirement for efficient polymerization.
  • a latex polymer can be formed from the polymerization product of the fatty amide(meth)acrylate monomer and an ethylenically unsaturated monomer suitable for forming a latex composition.
  • Suitable ethylenically unsaturated monomers include vinyl acetate, vinyl chloride, vinyl ester of a saturated tertiary branched carboxylic acid, acrylonitrile, acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylic acid, methacrylic acid, butyl acrylate, butyl methacrylate, methyl methacrylate, methyl acrylate, p-acetoxystyrene, and styrene.
  • a three-neck, 1000 mL round bottom flask was purged with nitrogen once equipped with mechanical stirrer, thermometer, condenser and was charged with 500 g soybean oil. Nitrogen was bubbled through the oil overnight to deoxygenate the oil.
  • the flask was placed in an oil bath at 80° C., and 50 g of a sodium methoxide methanol solution (25% in methanol) was added to the flask.
  • the reaction mixture was equilibrated to 80° C., and 125.46 g of N-methyl ethanolamine was added to the flask. An exotherm of approximately 10° C. was noted. The reaction was maintained and the reaction progress was monitored by Fourier transform infrared spectroscopy (FTIR).
  • FTIR Fourier transform infrared spectroscopy
  • a three-neck, 1000 mL round bottom flask was purged with nitrogen once equipped with mechanical stirrer, thermometer, condenser and was charged with 500 g soybean oil. Nitrogen was bubbled into the mixture overnight to deoxygenate the oil.
  • the flask was placed in an oil bath at 80° C., and 50 g of a sodium methoxide methanol solution (25% in methanol) was added to the flask.
  • the reaction mixture was equilibrated to 80° C., and 186.05 g of ethanolamine was added to the flask. An exotherm of approximately 10° C. was noted. The reaction was maintained and the reaction progress was monitored by Fourier transform infrared spectroscopy (FTIR).
  • FTIR Fourier transform infrared spectroscopy
  • a three-neck, 1000 mL round bottom flask was purged with nitrogen after being equipped with a mechanical stirrer, thermometer, condenser and was charged with 500 g coconut oil. Nitrogen was bubbled through the oil overnight to deoxygenate the oil.
  • the flask was placed in an oil bath at 80° C., and 50 g of a sodium methoxide methanol solution (25% in methanol) was added to the flask.
  • the reaction mixture was equilibrated to 80° C., and 125.46 g of N-methyl ethanolamine was added to the flask. An exotherm was noted.
  • the reaction was maintained at 80° C. and the reaction progress was monitored by FTIR. Complete conversion was observed after 4 hours.
  • the reactor was then cooled to ambient conditions and 100 g of methylene chloride was added to the flask. The contents were washed three times with 500 mL of brine (5% sodium chloride). The aqueous phase was discarded and the organic phase was dried with magnesium sulfate. Methylene chloride was removed under reduced pressure, and the product (CocoA-1) was characterized by GPC, HPLC, and NMR spectroscopy.
  • a three-neck, 1000 mL round bottom flask equipped with thermometer, mechanical stirrer, and addition funnel was charged with 401.62 g of CocoA-1, 100.00 mL of methylene chloride, and 120.40 g of triethylamine.
  • the flask was placed in an ice bath and equilibrated to 0° C. 107.69 g of acryloyl chloride was charged to the addition funnel, and added dropwise into the flask over 4 hours.
  • the flask was allowed to equilibrate to ambient conditions overnight.
  • the contents were washed 5 times with 500 mL of brine (5% sodium chloride) to remove unreacted acryloyl chloride, triethylamine, and hydrochloric acid.
  • the aqueous phase was discarded and the organic phase was dried with magnesium sulfate.
  • Methylene chloride was removed under reduced pressure, and the product (CocoAA-1) was characterized by GPC, HPLC, and N
  • a three-neck, 1000 mL round bottom flask purged with nitrogen was equipped with mechanical stirrer, thermometer, condenser and was charged with 250 g coconut oil. Nitrogen was bubbled through the oil overnight to deoxygenate the oil.
  • the flask was placed in an oil bath at 80° C., and 25 g of a sodium methoxide methanol solution (25% in methanol) was added to the flask.
  • the reaction mixture was equilibrated to 80° C., and 63.78 g of N-methyl ethanolamine was added to the flask. An exotherm was noted.
  • the reaction was maintained at 80° C. and the reaction progress was monitored by FTIR. Complete conversion was observed after 4 hours.
  • the reactor was cooled to ambient conditions and 100 g of methylene chloride was added to the flask. The contents were washed three times with 500 mL of brine (5% sodium chloride). The aqueous phase was discarded and the organic phase was dried with magnesium sulfate. Methylene chloride was removed under reduced pressure, and the product (LinA-1) was characterized by GPC, HPLC, and NMR spectroscopy.
  • a three-neck, 1000 mL round bottom flask was purged with nitrogen while equipped with mechanical stirrer, thermometer, condenser and was charged with 150.00 g of soybean oil and 150.00 g of tung oil. Nitrogen was bubbled through the oil overnight to deoxygenate the oil.
  • the flask was placed in an oil bath at 80° C., and 24 g of a sodium methoxide methanol solution (25% in methanol) was added to the flask.
  • the reaction mixture was equilibrated to 80° C., and 125.46 g of N-methyl ethanolamine was added to the flask. An exotherm of approximately 10° C. was noted. The reaction was maintained at 80° C. and the progress was monitored by FTIR.
  • a three-neck, 500 mL round bottom flask equipped with thermometer, mechanical stirrer, and addition funnel was charged with 250.00 g of Soy-TungA-1, 100.00 mL of methylene chloride, and 74.94 g of triethylamine.
  • the flask was placed in an ice bath and equilibrated to 0° C. 67.03 g of acryloyl chloride was charged to the addition funnel, and added dropwise into the flask over 2 hours. The flask was allowed to equilibrate to ambient conditions overnight.
  • the reactor contents were washed 5 times with 500 mL of brine (5% sodium chloride) to remove unreacted acryloyl chloride, triethylamine, and hydrochloric acid.
  • the aqueous phase was discarded and the organic phase was dried with magnesium sulfate.
  • Methylene chloride was removed under reduced pressure, and the product (SoyTung AA-1) was characterized by GPC, HPLC, and NMR spectroscopy.
  • a 1 L kettle was charged with 130.00 g of deionized (DI) water and 1.21 g of Rhodapex® CO-436, purged with nitrogen for 15 minutes, and stirred while heating to 70° C.
  • the seed was prepared by preemulsifying a mixture of DI water (8.80 g), Rhodapex CO-436 (0.55 g), Igepal® CO-887 (0.20 g), butyl acrylate (8.20 g), methyl methacrylate (6.30 g), and methacrylic acid (0.10 g) at 1,800 rpm for 20 minutes, and was transferred to the kettle.
  • Ammonium persulfate (2.80 g) was dissolved in 30.00 g of DI water and 3.3 mL of this solution was added to the kettle. Meanwhile, a monomer feed was prepared by preemulsifying a mixture of DI water (160.00 g), sodium bicarbonate (1.65 g), Rhodapex CO-436 (6.00 g), Igepal CO-887 (5.00 g), butyl acrylate (150.00 g), methyl methacrylate (170.00 g), and methacrylic acid (6.00 g) at 1,800 rpm for 20 minutes. The monomer feed was added to the kettle over 2 hours while the remaining initiator solution was added over a period of 2.25 hours. After complete addition, the reaction was allowed to continue at 70° C. for 4 hours.
  • chaser solutions were prepared—one by dissolving t-butyl hydroperoxide (0.36 g) in 10.00 g of DI water and the other by dissolving sodium bisulfite (0.35 g) in 10.00 g of DI water. Both chaser solutions were fed to the kettle over a period of 1 hour, and the emulsion was allowed to cool to ambient temperature and discharged.
  • a 1 L kettle was charged with 130.00 g of DI water and 1.21 g of Rhodapex CO-436, purged with nitrogen for 15 minutes, and stirred while heating to 70° C.
  • the seed was prepared by preemulsifying a mixture of DI water (8.80 g), Rhodapex CO-436 (0.55 g), Igepal CO-887 (0.20 g), butyl acrylate (8.20 g), methyl methacrylate (6.30 g), and methacrylic acid (0.10 g) at 1,800 rpm for 20 minutes, and was transferred to the kettle.
  • Ammonium persulfate (2.80 g) was dissolved in 30.00 g of DI water and 3.3 mL of this solution was added to the kettle.
  • a monomer feed was prepared by preemulsifying a mixture of DI water (160.00 g), sodium bicarbonate (1.65 g), Rhodapex CO-436 (6.00 g), Igepal CO-887 (5.00 g), butyl acrylate (85.00 g), methyl methacrylate (170.00 g), SoyAA-1 (65.00 g), and methacrylic acid (6.00 g) at 1,800 rpm for 20 minutes.
  • the monomer feed was added to the kettle over 2 hours while the remaining initiator solution was added over a period of 2.25 hours. After complete addition, the reaction was allowed to continue at 70° C. for 4 hours.
  • Two chaser solutions were prepared - one by dissolving t-butyl hydroperoxide (0.36 g) in 10.00 g of DI water and the other by dissolving sodium bisulfite (0.35 g) in 10.00 g of DI water. Both chaser solutions were fed to the kettle over a period of 1 hour, and the emulsion was allowed to cool to ambient temperature and discharged.
  • a 500 mL kettle was charged with 110.00 g of DI water and 0.80 g of Rhodapex CO-436, purged with nitrogen for 15 minutes, and stirred while heating to 70° C.
  • the seed was prepared by preemulsifying a mixture of DI water (6.00 g), Rhodapex CO-436 (0.37 g), Igepal CO-887 (0.13 g), butyl acrylate (5.50 g), methyl methacrylate (4.20 g), and methacrylic acid (0.07 g) at 1,800 rpm for 20 minutes, and was transferred to the kettle.
  • Ammonium persulfate (2.80 g) was dissolved in 30.00 g of DI water and 3.3 mL of this solution was added to the kettle.
  • the monomer feed was prepared by preemulsifying a mixture of DI water (107.00 g), sodium bicarbonate (1.10 g), Rhodapex CO-436 (4.00 g), Igepal CO-887 (3.33 g), butyl acrylate (74.70 g), methyl methacrylate (82.70 g), styrene (20.00 g), methacrylic acid (4.00 g), diacetone acrylamide (3.08 g), and SoyAA-1 (36.00 g) at 1,800 rpm for 20 minutes.
  • the monomer feed was added to the kettle over 2 hours while the remaining initiator solution was added over a period of 2.25 hours. After complete addition, the reaction was allowed to continue at 70° C. for 4 hours.
  • Two chaser solutions were prepared - one by dissolving t-butyl hydroperoxide (0.36 g) in 10.00 g of DI water and the other by dissolving sodium bisulfite (0.35 g) in 10.00 g of DI water. Both chaser solutions were fed to the kettle over a period of 1 hour. The emulsion was allowed to cool to ambient temperature and the pH was adjusted to 9 by adding ammonia followed by adipic dihydrazide solution (4.6 g in 11.00 g of DI water).
  • a 500 mL kettle was charged with 110.00 g of DI water and 0.80 g of Rhodapex CO-436, purged with nitrogen for 15 minutes, and stirred while heating to 70° C.
  • the seed was prepared by preemulsifying a mixture of DI water (6.00 g), Rhodapex CO-436 (0.37 g), Igepal CO-887 (0.13 g), butyl acrylate (5.50 g), methyl methacrylate (4.20 g), and methacrylic acid (0.07 g) at 1,800 rpm for 20 minutes, and was transferred to the kettle.
  • Ammonium persulfate (2.80 g) was dissolved in 30.00 g of DI water and 3.3 mL of this solution was added to the kettle.
  • the monomer feed was prepared by preemulsifying a mixture of DI water (107.00 g), sodium bicarbonate (1.10 g), Rhodapex CO-436 (4.00 g), Igepal CO-887 (3.33 g), butyl acrylate (74.70 g), methyl methacrylate (82.70 g), styrene (20.00 g), methacrylic acid (4.00 g), diacetone acrylamide (3.08 g), and LinAA-1 (36.00 g) at 1,800 rpm for 20 minutes.
  • the monomer feed was added to the kettle over 2 hours while the remaining initiator solution was added over a period of 2.25 hours. After complete addition, the reaction was allowed to continue at 70° C. for 4 hours.
  • Two chaser solutions were prepared - one by dissolving t-butyl hydroperoxide (0.36 g) in 10.00 g of DI water and the other by dissolving sodium bisulfite (0.35 g) in 10.00 g of DI water. Both chaser solutions were fed to the kettle over a period of 1 hour. The emulsion was allowed to cool to ambient temperature and the pH was adjusted to 9 by adding ammonia followed by adipic dihydrazide solution (4.6 g in 11.00 g of DI water).

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Abstract

The present invention is directed to a fatty amide (meth)acrylate monomer, methods of making the monomer, and latex polymers comprising the fatty amide (meth)acrylate monomer. The monomers are derived by reacting unsaturated vegetable oils with ethanolamine or substituted ethanolamine. The vegetable oil derivative is then reacted with either (meth)acryloyl chloride or (meth)acrylic acid to form a fatty amide (meth)acrylate monomer or the product of the reaction of hydroxyethyl(meth)acrylate reacted with isophorone diisocyanate to form a urethane fatty amide(meth)acrylate monomer. The increased hydrophilicity of the fatty amide(meth)acrylate monomer facilitates the diffusion through the aqueous phase. The monomer synthesis is designed to be glycerol ester-free to increase long term stability for monomers and polymers.

Description

    BACKGROUND OF THE INVENTION
  • The present invention is directed to vegetable oil derivatives. More particularly, the present invention is directed to functionalized vegetable oil derivative macromonomers that can be used in latexes and coatings.
  • A key problem encountered by coatings manufacturers is the development of coating formulations with low volatile organic compound (VOC) content. For instance, emulsion polymers are currently formulated with coalescing aids or plasticizers in order to form films at and below ambient conditions yet dry to films of sufficient glass transition temperature (Tg) to perform adequately at and above room temperature. However, the coalescing aids evaporate upon application and constitute VOCs. In general, the ability of emulsion polymers to form or coalesce into a smooth film is governed by the minimum film temperature (MFT) of the polymer in question. Low MFT polymers are required in order to exhibit coalescence, flow, and surface wetting properties. However, if the polymer remains soft and tacky, the coatings are not usable. Therefore, it is necessary to develop a technology in which coating formulations contain suitable ingredients to provide an initial low MFT, which, upon application, form non-tacky, durable, hard, and water resistant surfaces having a Tg significantly above their MFT.
  • Various coating compositions which cure under ambient conditions are known in the prior art. A few such examples involve curing by a chemical reaction such as epoxide-carboxylic acid reaction, isocyanate-moisture reaction, polyaziridine-carboxylic acid reaction, and activated methylene-unsaturated acrylic reaction.
  • Recently, a number of new latex or emulsion compositions derived from semi-drying and/or non-drying oils have been developed for use in coatings, adhesives and inks. Such compositions are disclosed in U.S. Pat. Nos. 6,001,913; 6,174,948; and 6,203,720 each of which is incorporated herein by reference in its entirety. The inherent hydrophobicity of vegetable oil macromonomers (VOMMs) limits their ability to migrate through the aqueous phase during emulsion polymerization and results in less than random copolymerizability. The VOMMs are likely to remain in the monomer droplets unlike the smaller less hydrophobic comonomers that diffuse through the aqueous phase and randomly polymerize within particles. Eventually, the unpolymerized VOMM droplets coalesce and form a separate phase as they are incompatible with the water and latex particles. It would therefore be an advancement to develop VOMMs with more hydrophilicity to facilitate/promote VOMM diffusion through the aqueous phase. Moreover, long-term storage stability of monomers and polymers is decreased when monomers are synthesized with glycerol esters as esters are susceptible to hydrolysis. It would thus be an additional benefit to synthesize the monomers in the absence of glycerol ester groups to increase long term stability for monomers and polymers.
  • The search for additional compositions that can be used in latexes and coatings is continuing. Accordingly, it would be an advancement in the art to provide glycerol ester-free compositions made from renewable resources that are suitable for use in latexes and coatings.
    • SUMMARY OF THE INVENTION
  • The present invention is directed to functionalized vegetable oil derivatives which are useful in latexes and coatings. In one embodiment, an ethylenically unsaturated vegetable oil is reacted with ethanolamine or substituted ethanolamines to form the hydroxy functional fatty amide. The modified vegetable oil is then reacted with (meth)acryloyl chloride, or the corresponding (meth)acrylic acid to form a fatty amide(meth)acrylate monomer. In another embodiment, the modified vegetable oil can be reacted with the product of the reaction of hydroxyethyl(meth)acrylate reacted with isophorone diisocyanate to form a urethane fatty amide(meth)acrylate monomer. The functionalized vegetable oil derivatives can be formulated into latexes and other coating compositions.
  • The present invention provides vegetable oil derivatives that are more hydrophilic than vegetable oils and are designed specifically for efficient random emulsion copolymerization. Specifically, the present invention provides glycerol ester-free fatty amide(meth)acrylate monomers.
  • The present invention is directed to a fatty amide(meth)acrylate monomer of the formula:
  • Figure US20080183000A1-20080731-C00001
  • The present invention is also directed to a latex polymer comprising the polymerization product of an ethylenically unsaturated monomer suitable for forming a latex composition and the modified fatty amide monomer. The present invention also provides a method of making a modified fatty amide monomer comprising the reaction product of a vegetable oil and ethanolamine or substituted ethanolamine; and a (meth)acrylate selected from the group comprising: (meth)acryloyl chloride, (meth)acrylic acid, and the product of hydroxyethyl(meth)acrylate reacted in equimolar proportion with isophorone diisocyanate.
    • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • The present invention is directed to a series of vegetable oil macromonomers and their use in latexes and coatings. The invention is also directed to the method of producing these macromonomers. The monomers are derived by reacting unsaturated vegetable oils with ethanolamine or substituted ethanolamine. The vegetable oil derivative is then reacted with either (meth)acryloyl chloride or (meth)acrylic acid to form a fatty amide(meth)acrylate monomer or the product of the reaction of hydroxyethyl(meth)acrylate reacted with isophorone diisocyanate to form a urethane fatty amide(meth)acrylate monomer.
  • In a preferred embodiment, a vegetable oil such as soybean oil, coconut oil, or linseed oil is reacted with ethanolamine (or substituted ethanolamine) followed by reaction with (meth)acryloyl chloride or (meth)acrylic acid to form the fatty amide(meth)acrylate monomer. Examples of substituted ethanolamines include N-methyl ethanolamine, N-oleoylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-tert-butylethanolamine, N-(tert-butoxycarbonyl)ethanolamine, N-(allyloxycarbonyl) ethanolamine, benzyl N-(2-hydroxyethyl)carbamate, ethyl-N-(2-hydroxyethyl)-carbamate, and diethanolamine. The reaction mechanism is schematically shown in Reaction 1.
  • Figure US20080183000A1-20080731-C00002
  • Any vegetable oil can be used in the present invention. However, linseed oil, soybean oil and coconut oil are preferred.
  • Various compounds can be used to modify the fatty amide. Examples include but are not limited to (meth)acryloyl chloride and (meth)acrylic acid.
  • In another preferred embodiment, urethane fatty amide monomers are synthesized. First, hydroxyethyl(meth)acrylate is reacted with isophorone diisocyanate. In a preferred embodiment, the hydroxyl(meth)acrylate is reacted in equimolar proportion with isophorone diisocyanate. In a separate reaction, a vegetable oil, for example, soybean oil, coconut oil, or linseed oil is reacted with ethanolamine (or substituted ethanolamine) to form the hydroxyl functional fatty amide. The products of the two reactions were reacted to form the urethane fatty amide(meth)acrylate monomer schematically shown in Reaction 2.
  • Figure US20080183000A1-20080731-C00003
  • The macromonomers of the present invention can be used to make latexes and coatings compositions. The monomers described in this patent application can be polymerized in a single or multi- stage emulsion polymerization process to include macroemulsion, miniemulsion, microemulsion and processing can be batch, semi-batch or continuous. Although it is possible to use this monomer in a staged emulsion polymerization, as disclosed in published U.S. Application 2003/0045609, the teachings of which are hereby incorporated by reference, it is not a requirement for efficient polymerization. A latex polymer can be formed from the polymerization product of the fatty amide(meth)acrylate monomer and an ethylenically unsaturated monomer suitable for forming a latex composition. Suitable ethylenically unsaturated monomers include vinyl acetate, vinyl chloride, vinyl ester of a saturated tertiary branched carboxylic acid, acrylonitrile, acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylic acid, methacrylic acid, butyl acrylate, butyl methacrylate, methyl methacrylate, methyl acrylate, p-acetoxystyrene, and styrene.
  • The invention is further understood by reference to the following examples which describe the formation of various macromonomers as well as the formulation of latexes and coatings.
    • EXAMPLES Example 1 SoyA-1
  • A three-neck, 1000 mL round bottom flask was purged with nitrogen once equipped with mechanical stirrer, thermometer, condenser and was charged with 500 g soybean oil. Nitrogen was bubbled through the oil overnight to deoxygenate the oil. The flask was placed in an oil bath at 80° C., and 50 g of a sodium methoxide methanol solution (25% in methanol) was added to the flask. The reaction mixture was equilibrated to 80° C., and 125.46 g of N-methyl ethanolamine was added to the flask. An exotherm of approximately 10° C. was noted. The reaction was maintained and the reaction progress was monitored by Fourier transform infrared spectroscopy (FTIR). Complete conversion via FTIR was observed after 4 hours. The reactor was cooled to ambient conditions and diluted with 100 g of methylene chloride. The contents were washed three times with 500 mL of brine (5% sodium chloride). The aqueous phase was discarded and the organic phase was dried with magnesium sulfate. Methylene chloride was removed under reduced pressure, and the product (SoyA-1) was characterized by gel permeation chromatography (GPC), high pressure liquid chromatography (HPLC), and nuclear magnetic resonance (NMR) spectroscopy.
    • Example 2 SoyA-2
  • A three-neck, 1000 mL round bottom flask was purged with nitrogen once equipped with mechanical stirrer, thermometer, condenser and was charged with 500 g soybean oil. Nitrogen was bubbled into the mixture overnight to deoxygenate the oil. The flask was placed in an oil bath at 80° C., and 50 g of a sodium methoxide methanol solution (25% in methanol) was added to the flask. The reaction mixture was equilibrated to 80° C., and 186.05 g of ethanolamine was added to the flask. An exotherm of approximately 10° C. was noted. The reaction was maintained and the reaction progress was monitored by Fourier transform infrared spectroscopy (FTIR). Complete conversion via FTIR was observed after 4 hours. The reactor was cooled to ambient conditions and diluted with 100 g of methylene chloride. The contents were washed three times with 500 mL of brine (5% sodium chloride). The aqueous phase was discarded and the organic phase was dried with magnesium sulfate. Methylene chloride was removed under reduced pressure, and the product (SoyA-2) was characterized by GPC, HPLC, and NMR spectroscopy.
    • Example 3 SoyAA-1
  • A three-neck, 1000 mL round bottom flask equipped with thermometer, mechanical stirrer, and addition funnel was charged with 250.00 g of SoyA-1, 100.00 mL of methylene chloride, and 74.94 g of triethylamine. The flask was placed in an ice bath and equilibrated to 0° C. 70.00 g of acryloyl chloride was charged to the addition funnel, and added dropwise into the flask over 4 hours. The flask was allowed to equilibrate to ambient conditions overnight. The contents were washed 5 times with 500 mL of brine (5% sodium chloride) to remove unreacted acryloyl chloride, triethylamine, and hydrochloric acid. The aqueous phase was discarded and the organic phase was dried with magnesium sulfate. Methylene chloride was removed under reduced pressure, and the product (SoyAA-1) was characterized by GPC, HPLC, and NMR spectroscopy.
    • Example 4 SoyAA-2
  • A three-neck, 1000 mL round bottom flask equipped with thermometer, mechanical stirrer, and addition funnel was charged with 250.00 g of SoyA-2, 100.00 mL of methylene chloride, and 78.19 g triethylamine. The flask was placed in an ice bath and equilibrated to 0° C. 70.00 g of acryloyl chloride was charged to the addition funnel, and added dropwise into the flask over 4 hours. The flask was allowed to equilibrate to ambient conditions overnight. The reactor contents were washed 5 times with 500 mL of brine (5% sodium chloride) to remove unreacted acryloyl chloride, triethylamine, and hydrochloric acid. The aqueous phase was discarded and the organic phase was dried with magnesium sulfate. Methylene chloride was removed under reduced pressure, and the product (SoyAA-2) was characterized by GPC, HPLC, and NMR spectroscopy.
    • Example 5 CocoA-1
  • A three-neck, 1000 mL round bottom flask was purged with nitrogen after being equipped with a mechanical stirrer, thermometer, condenser and was charged with 500 g coconut oil. Nitrogen was bubbled through the oil overnight to deoxygenate the oil. The flask was placed in an oil bath at 80° C., and 50 g of a sodium methoxide methanol solution (25% in methanol) was added to the flask. The reaction mixture was equilibrated to 80° C., and 125.46 g of N-methyl ethanolamine was added to the flask. An exotherm was noted. The reaction was maintained at 80° C. and the reaction progress was monitored by FTIR. Complete conversion was observed after 4 hours. The reactor was then cooled to ambient conditions and 100 g of methylene chloride was added to the flask. The contents were washed three times with 500 mL of brine (5% sodium chloride). The aqueous phase was discarded and the organic phase was dried with magnesium sulfate. Methylene chloride was removed under reduced pressure, and the product (CocoA-1) was characterized by GPC, HPLC, and NMR spectroscopy.
    • Example 6 CocoAA-1
  • A three-neck, 1000 mL round bottom flask equipped with thermometer, mechanical stirrer, and addition funnel was charged with 401.62 g of CocoA-1, 100.00 mL of methylene chloride, and 120.40 g of triethylamine. The flask was placed in an ice bath and equilibrated to 0° C. 107.69 g of acryloyl chloride was charged to the addition funnel, and added dropwise into the flask over 4 hours. The flask was allowed to equilibrate to ambient conditions overnight. The contents were washed 5 times with 500 mL of brine (5% sodium chloride) to remove unreacted acryloyl chloride, triethylamine, and hydrochloric acid. The aqueous phase was discarded and the organic phase was dried with magnesium sulfate. Methylene chloride was removed under reduced pressure, and the product (CocoAA-1) was characterized by GPC, HPLC, and NMR spectroscopy.
    • Example 7 SoyUA-1
  • A three-neck, 500 mL round bottom flask equipped with thermometer, mechanical stirrer, and addition funnel was charged with 64.44 g isophorone diisocyanate and 0.02 g dibutyl tin dilaurate. 33.64 g hydroxyl ethyl acrylate was charged to the addition funnel and added dropwise to the flask over 4 hours. Next, the addition funnel was charged with 100.00 g SoyA-1, and added to the flask over 1 hour. The reaction progress was monitored by FTIR, and deemed complete when residual isocyanate could not be identified in the FTIR spectra. The product (SoyUA-1) was characterized by GPC, HPLC, and NMR spectroscopy.
    • Example 8 LinA-1
  • A three-neck, 1000 mL round bottom flask purged with nitrogen was equipped with mechanical stirrer, thermometer, condenser and was charged with 250 g coconut oil. Nitrogen was bubbled through the oil overnight to deoxygenate the oil. The flask was placed in an oil bath at 80° C., and 25 g of a sodium methoxide methanol solution (25% in methanol) was added to the flask. The reaction mixture was equilibrated to 80° C., and 63.78 g of N-methyl ethanolamine was added to the flask. An exotherm was noted. The reaction was maintained at 80° C. and the reaction progress was monitored by FTIR. Complete conversion was observed after 4 hours. The reactor was cooled to ambient conditions and 100 g of methylene chloride was added to the flask. The contents were washed three times with 500 mL of brine (5% sodium chloride). The aqueous phase was discarded and the organic phase was dried with magnesium sulfate. Methylene chloride was removed under reduced pressure, and the product (LinA-1) was characterized by GPC, HPLC, and NMR spectroscopy.
    • Example 9 LinAA-1
  • A three-neck, 500 mL round bottom flask equipped with thermometer, mechanical stirrer, and addition funnel was charged with 200.00 g of LinA-1, 100.00 mL of methylene chloride, and 60.00 g of triethylamine. The flask was placed in an ice bath and equilibrated to 0° C. 60.00 g of acryloyl chloride was charged to the addition funnel, and added dropwise into the flask over 2 hours. The flask was allowed to equilibrate to ambient conditions overnight. The contents were washed 5 times with 500 mL of brine (5% sodium chloride) to remove unreacted acryloyl chloride, triethylamine, and hydrochloric acid. The aqueous phase was discarded and the organic phase was dried with magnesium sulfate. Methylene chloride was removed under reduced pressure, and the product (LinAA-1) was characterized by GPC, HPLC, and NMR spectroscopy.
    • Example 10 SoyMA-1
  • A three-neck, 1000 mL round bottom flask equipped with thermometer, mechanical stirrer, and addition funnel was charged with 200.00 g of SoyA-1, 100.00 mL of methylene chloride, and 55.06 g of triethylamine. The flask was placed in an ice bath and equilibrated to 0° C. 49.25 g of methacryloyl chloride was charged to the addition funnel, and added dropwise into the flask over 2 hours. The flask was allowed to equilibrate to ambient conditions overnight. The reactor contents were washed 5 times with 500 mL of brine (5% sodium chloride) to remove unreacted acryloyl chloride, triethylamine, and hydrochloric acid. The aqueous phase was discarded and the organic phase was dried with magnesium sulfate. Methylene chloride was removed under reduced pressure, and the product (SoyMA-1) was characterized by GPC, HPLC, and NMR spectroscopy.
    • Example 11 SoyAA-1 Esterification via Acrylic Acid
  • A 500 mL round bottom flask was charged with 100.0 g SoyA-1, 21.5 g acrylic acid, and 100.0 g toluene. The mixture was heated to 100° C. and 2.5 g methane sulfonic acid was added. The reaction was continued until no further water was released. The toluene was removed under reduced pressure to yield SoyAA-1 and characterized by GPC, HPLC, and NMR spectroscopy.
    • Example 12 LinUA-1
  • A three-neck, 1000 mL round bottom flask equipped with thermometer, mechanical stirrer, and addition funnel was charged with 111.11 g isophorone diisocyanate, 60.0 g hexane, 0.17 g phenothiazine (PTZ), 0.17 g methyl hydroquinone (MeHQ) and 0.02 g dibutyl tin dilaurate. 58.00 g hydroxyl ethyl acrylate was charged to the addition funnel and added dropwise to the flask over 2 hours. The temperature was raised to 65° C. and 168.78 g of LinA-1 was added to the flask through the addition funnel over 1 hour. The reaction progress was monitored by FTIR, and deemed complete when residual isocyanate could not be identified in the FTIR spectra. The hexane was removed under reduced pressure, and the product (LinUA-1) was characterized by GPC, HPLC, and NMR spectroscopy.
    • Example 13 Soy-TungA-1
  • A three-neck, 1000 mL round bottom flask was purged with nitrogen while equipped with mechanical stirrer, thermometer, condenser and was charged with 150.00 g of soybean oil and 150.00 g of tung oil. Nitrogen was bubbled through the oil overnight to deoxygenate the oil. The flask was placed in an oil bath at 80° C., and 24 g of a sodium methoxide methanol solution (25% in methanol) was added to the flask. The reaction mixture was equilibrated to 80° C., and 125.46 g of N-methyl ethanolamine was added to the flask. An exotherm of approximately 10° C. was noted. The reaction was maintained at 80° C. and the progress was monitored by FTIR. Complete conversion was observed after 4 hours. The reactor was then cooled to ambient conditions and 100 g of methylene chloride was added to the flask. The contents were washed three times with 500 mL of brine (5% sodium chloride). The aqueous phase was discarded and the organic phase was dried with magnesium sulfate. Methylene chloride was removed under reduced pressure, and the product (Soy-TungA-1) was characterized by GPC, HPLC, and NMR spectroscopy.
    • Example 14 Soy-TungAA-1
  • A three-neck, 500 mL round bottom flask equipped with thermometer, mechanical stirrer, and addition funnel was charged with 250.00 g of Soy-TungA-1, 100.00 mL of methylene chloride, and 74.94 g of triethylamine. The flask was placed in an ice bath and equilibrated to 0° C. 67.03 g of acryloyl chloride was charged to the addition funnel, and added dropwise into the flask over 2 hours. The flask was allowed to equilibrate to ambient conditions overnight. The reactor contents were washed 5 times with 500 mL of brine (5% sodium chloride) to remove unreacted acryloyl chloride, triethylamine, and hydrochloric acid. The aqueous phase was discarded and the organic phase was dried with magnesium sulfate. Methylene chloride was removed under reduced pressure, and the product (SoyTung AA-1) was characterized by GPC, HPLC, and NMR spectroscopy.
    • Example 15 Control Latex
  • A 1 L kettle was charged with 130.00 g of deionized (DI) water and 1.21 g of Rhodapex® CO-436, purged with nitrogen for 15 minutes, and stirred while heating to 70° C. The seed was prepared by preemulsifying a mixture of DI water (8.80 g), Rhodapex CO-436 (0.55 g), Igepal® CO-887 (0.20 g), butyl acrylate (8.20 g), methyl methacrylate (6.30 g), and methacrylic acid (0.10 g) at 1,800 rpm for 20 minutes, and was transferred to the kettle. Ammonium persulfate (2.80 g) was dissolved in 30.00 g of DI water and 3.3 mL of this solution was added to the kettle. Meanwhile, a monomer feed was prepared by preemulsifying a mixture of DI water (160.00 g), sodium bicarbonate (1.65 g), Rhodapex CO-436 (6.00 g), Igepal CO-887 (5.00 g), butyl acrylate (150.00 g), methyl methacrylate (170.00 g), and methacrylic acid (6.00 g) at 1,800 rpm for 20 minutes. The monomer feed was added to the kettle over 2 hours while the remaining initiator solution was added over a period of 2.25 hours. After complete addition, the reaction was allowed to continue at 70° C. for 4 hours. Two chaser solutions were prepared—one by dissolving t-butyl hydroperoxide (0.36 g) in 10.00 g of DI water and the other by dissolving sodium bisulfite (0.35 g) in 10.00 g of DI water. Both chaser solutions were fed to the kettle over a period of 1 hour, and the emulsion was allowed to cool to ambient temperature and discharged.
    • Example 16 SoyAA-1 Latex
  • A 1 L kettle was charged with 130.00 g of DI water and 1.21 g of Rhodapex CO-436, purged with nitrogen for 15 minutes, and stirred while heating to 70° C. The seed was prepared by preemulsifying a mixture of DI water (8.80 g), Rhodapex CO-436 (0.55 g), Igepal CO-887 (0.20 g), butyl acrylate (8.20 g), methyl methacrylate (6.30 g), and methacrylic acid (0.10 g) at 1,800 rpm for 20 minutes, and was transferred to the kettle. Ammonium persulfate (2.80 g) was dissolved in 30.00 g of DI water and 3.3 mL of this solution was added to the kettle. Meanwhile, a monomer feed was prepared by preemulsifying a mixture of DI water (160.00 g), sodium bicarbonate (1.65 g), Rhodapex CO-436 (6.00 g), Igepal CO-887 (5.00 g), butyl acrylate (85.00 g), methyl methacrylate (170.00 g), SoyAA-1 (65.00 g), and methacrylic acid (6.00 g) at 1,800 rpm for 20 minutes. The monomer feed was added to the kettle over 2 hours while the remaining initiator solution was added over a period of 2.25 hours. After complete addition, the reaction was allowed to continue at 70° C. for 4 hours. Two chaser solutions were prepared - one by dissolving t-butyl hydroperoxide (0.36 g) in 10.00 g of DI water and the other by dissolving sodium bisulfite (0.35 g) in 10.00 g of DI water. Both chaser solutions were fed to the kettle over a period of 1 hour, and the emulsion was allowed to cool to ambient temperature and discharged.
    • Example 17 Semi-Gloss Coatings
  • The latexes described in Examples 15 and 16 were formulated into semi-gloss coatings as per the formulation shown in Table 2.
  • TABLE 2
    Semi-gloss Coating
    Ingredient Weight (g)
    Grind
    Water 225.00
    Natrosol Plus ® 330 2.00
    Potassium carbonate 1.00
    Tamol ® 731A 10.00
    Triton ® CF-10 2.00
    Kathon LX ® 1.5% 1.50
    Ti-Pure ® 706 240.00
    Polygloss ® 90 20.00
    Attagel ® 50 4.00
    Letdown
    Water 60.00
    Drewplus ® L-475 3.00
    Drewthix ® 864 2.00
    Aquaflow NHS ® 300 12.00
    Latex 500.00

    The coatings were evaluated for their performance properties and the results are listed in Table 3.
  • TABLE 3
    Coating Properties
    Property Control Coating SoyAA-1 Coating
    ICI viscosity, Poises 0.51 0.55
    Stormer viscosity, KU 109 106
    Scrub resistance (1 week) 362 569
    Adhesion (1 week) 2B 3.5B
    Gloss (60°) 27.3 20.9
    Wet adhesion (1 week) >1200 >1200
    • Example 18 SoyAA-1 Latex with Diacetone Acrylamide
  • A 500 mL kettle was charged with 110.00 g of DI water and 0.80 g of Rhodapex CO-436, purged with nitrogen for 15 minutes, and stirred while heating to 70° C. The seed was prepared by preemulsifying a mixture of DI water (6.00 g), Rhodapex CO-436 (0.37 g), Igepal CO-887 (0.13 g), butyl acrylate (5.50 g), methyl methacrylate (4.20 g), and methacrylic acid (0.07 g) at 1,800 rpm for 20 minutes, and was transferred to the kettle. Ammonium persulfate (2.80 g) was dissolved in 30.00 g of DI water and 3.3 mL of this solution was added to the kettle. Meanwhile, the monomer feed was prepared by preemulsifying a mixture of DI water (107.00 g), sodium bicarbonate (1.10 g), Rhodapex CO-436 (4.00 g), Igepal CO-887 (3.33 g), butyl acrylate (74.70 g), methyl methacrylate (82.70 g), styrene (20.00 g), methacrylic acid (4.00 g), diacetone acrylamide (3.08 g), and SoyAA-1 (36.00 g) at 1,800 rpm for 20 minutes. The monomer feed was added to the kettle over 2 hours while the remaining initiator solution was added over a period of 2.25 hours. After complete addition, the reaction was allowed to continue at 70° C. for 4 hours. Two chaser solutions were prepared - one by dissolving t-butyl hydroperoxide (0.36 g) in 10.00 g of DI water and the other by dissolving sodium bisulfite (0.35 g) in 10.00 g of DI water. Both chaser solutions were fed to the kettle over a period of 1 hour. The emulsion was allowed to cool to ambient temperature and the pH was adjusted to 9 by adding ammonia followed by adipic dihydrazide solution (4.6 g in 11.00 g of DI water).
    • Example 19 LinAA-1 Latex with Diacetone Acrylamide
  • A 500 mL kettle was charged with 110.00 g of DI water and 0.80 g of Rhodapex CO-436, purged with nitrogen for 15 minutes, and stirred while heating to 70° C. The seed was prepared by preemulsifying a mixture of DI water (6.00 g), Rhodapex CO-436 (0.37 g), Igepal CO-887 (0.13 g), butyl acrylate (5.50 g), methyl methacrylate (4.20 g), and methacrylic acid (0.07 g) at 1,800 rpm for 20 minutes, and was transferred to the kettle. Ammonium persulfate (2.80 g) was dissolved in 30.00 g of DI water and 3.3 mL of this solution was added to the kettle. Meanwhile, the monomer feed was prepared by preemulsifying a mixture of DI water (107.00 g), sodium bicarbonate (1.10 g), Rhodapex CO-436 (4.00 g), Igepal CO-887 (3.33 g), butyl acrylate (74.70 g), methyl methacrylate (82.70 g), styrene (20.00 g), methacrylic acid (4.00 g), diacetone acrylamide (3.08 g), and LinAA-1 (36.00 g) at 1,800 rpm for 20 minutes. The monomer feed was added to the kettle over 2 hours while the remaining initiator solution was added over a period of 2.25 hours. After complete addition, the reaction was allowed to continue at 70° C. for 4 hours. Two chaser solutions were prepared - one by dissolving t-butyl hydroperoxide (0.36 g) in 10.00 g of DI water and the other by dissolving sodium bisulfite (0.35 g) in 10.00 g of DI water. Both chaser solutions were fed to the kettle over a period of 1 hour. The emulsion was allowed to cool to ambient temperature and the pH was adjusted to 9 by adding ammonia followed by adipic dihydrazide solution (4.6 g in 11.00 g of DI water).
    • REFERENCES
    • Thames, Shelby F.; Smith, Oliver W.; Evans, James M.; Dutta, Sandipan; Chen, Lianzhou. (University of Southern Mississippi, USA). Functionalized vegetable oil derivatives used in latex and coating compositions and their preparation. U.S. Pat. Appl. Publ. (2005), 10 pp. CODEN: USXXCO US 2005203246 A1 20050915 Patent written in English. Application: US 2004-800410 20040312. Priority:. CAN143:307794 AN2005:1004384 CAPLUS
    • Xu, Yuanhao; Liu, Fuchang; Wan, Zhong; Liu, Wenlin; Hou, Peimin. Aqueous acrylic acid-modified alkyd amino resin baking paints. Faming Zhuanli Shenqing Gongkai Shuomingshu (2003), 11 pp. CODEN: CNXXEV CN 1405254 A 20030326 CAN 142:200150 AN 2004:687257 CAPLUS
    • Thames, Shelby Freland; Wang, Zhiyu; Brister, Elizabeth H.; Hariharan, Rajan; King, Corey L.; Panjnani, Kamlesh Gopichand. Internally plasticized and low-VOC latex compositions and their applications. U.S. (2003), 25 pp., Cont.-in-part of U. S. Ser. No. 773,741. CODEN: USXXAM US 6624223 B1 20030923 CAN 139:262270 AN 2003:749999 CAPLUS
    • Thames, Shelby F.; Smith, Oliver W.; Chen, Sheng; Blackwell, Catherine C. Preparation of latex polymers containing ethylenically unsaturated derivatives of fatty acids and/or oils by two-stage emulsion polymerization. U.S. Pat. Appl. Publ. (2003), 9 pp., Cont.-in-part of U.S. Ser. No. 460,946. CODEN: USXXCO US 2003045609 A1 20030306 CAN 138:205825 AN 2003:174494 CAPLUS
    • Thames, Shelby Freland; Wang, Zhiyu; Hariharan, Rajan; Panjnani, Kamlesh Gopichand; Brister, Elizabeth H.; King, Corey L. Internally plasticized and low VOC latex compositions, ethylenically unsaturated carboxylate monomer, and their coating, adhesive or ink applications. PCT Int. Appl. (2001), 62 pp. CODEN: PIXXD2 WO 2001044380 A2 20010621 CAN 135:47673 AN2001:453182 CAPLUS
    • Bloom, Paul D. Epoxidized esters of vegetable oil fatty acids as reactive diluents. U.S. Pat. Appl. Publ. (2006), 19 pp. CODEN: USXXCO US 2006020062 A1 20060126 CAN 144:130749 AN2006:79094 CAPLUS
    • Bloom, Paul D.; Tabuena-Salyers, Teodora R. Thickening systems and aqueous coating compositions, and method for their manufacture and use. U.S. Pat. Appl. Publ. (2005), 17 pp. CODEN: USXXCO US 2005192383 A1 20050901 CAN 143:249817 AN 2005:963821 CAPLUS

Claims (17)

1. A modified fatty amide (meth)acrylate monomer of the formula:
Figure US20080183000A1-20080731-C00004
2. The fatty amide (meth)acrylate monomer of claim 1 wherein the fatty acid is derived from vegetable oil.
3. The fatty amide (meth)acrylate monomer of claim 1 wherein the fatty acid is oleic, linoleic, linolenic, caprylic, capric, lauric, palmitic, stearic or eleostearic acid.
4. A latex polymer comprising the polymerization product of:
an ethylenically unsaturated monomer suitable for forming a latex composition; and
the fatty amide (meth)acrylate monomer of claim 1.
5. The latex polymer of claim 4 wherein the fatty acid of the modified fatty amide (meth)acrylate monomer is derived from vegetable oil.
6. The latex polymer of claim 4 wherein the fatty acid of the modified fatty amide (meth)acrylate monomer is oleic, linoleic, linolenic, caprylic, capric, lauric, palmitic, stearic or eleostearic acid.
7. The latex polymer of claim 4 wherein said ethylenically unsaturated monomer is selected from the group consisting of vinyl acetate, vinyl chloride, vinyl ester of a saturated tertiary branched carboxylic acid, acrylonitrile, acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylic acid, methacrylic acid, butyl acrylate, butyl methacrylate, methyl methacrylate, methyl acrylate, para-acetoxystyrene, and styrene.
8. A method of making a fatty amide (meth)acrylate monomer by reacting:
the reaction product of a vegetable oil and ethanolamine or substituted ethanolamines; and
a (meth)acrylate functionalizing compound selected from the group comprising: acryloyl chloride, methacryloyl chloride, acrylic acid, methacrylic acid, and the product of hydroxyethyl (meth)acrylate reacted in equimolar proportion with isophorone diisocyanate.
9. The method of claim 8 wherein the vegetable oil is soybean oil, coconut oil or linseed oil.
10. The method of claim 8 where the substituted ethanolamine is N-methyl ethanolamine, N-oleoylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-tert-butylethanolamine, N-(tert-butoxycarbonyl)ethanolamine, N-(allyloxycarbonyl) ethanolamine, benzyl N-(2-hydroxyethyl)carbamate, ethyl-N-(2-hydroxyethyl)-carbamate, or diethanolamine.
11. A fatty amide (meth)acrylate monomer made by the method of claim 8.
12. The fatty amide (meth)acrylate monomer of claim 2 wherein the fatty acid is derived from vegetable oil selected from the group consisting of linseed oil, soybean oil, coconut oil, safflower oil and tung oil.
13. The fatty amide (meth)acrylate monomer of claim 1 wherein the fatty acid has at least 8 carbon atoms.
14. The fatty amide (meth)acrylate monomer of claim 1 wherein the fatty acid is unsaturated.
15. The latex polymer of claim 5 wherein the fatty acid is derived from vegetable oil selected from the group consisting of linseed oil, soybean oil, coconut oil, safflower oil and tung oil.
16. The latex polymer of claim 4 wherein the fatty acid has at least 8 carbon atoms.
17. The latex polymer of claim 4 wherein the fatty acid is unsaturated.
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US20090143527A1 (en) 2009-06-04

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